Anthraquinone dispersing agents

ABSTRACT

Dyestuffs of the formulae 
     
         D--Z--O--OC--X--O).sub.y H].sub.n 
    
     and 
     
         D--Z--O--OC--X--O).sub.(y.sub.-1) COT].sub.n 
    
     wherein D is the radical of an anthraquinone dyestuff which is attached to Z through a carbon atom of an aromatic ring present in D; Z is a divalent bridging group; n is a positive integer having a value of 1 to 4; X is a divalent saturated or unsaturated aliphatic radical containing at least 8 carbon atoms and in which there are at least 4 carbon atoms between the --CO-- and --O-- groups; T is a saturated or unsaturated aliphatic radical of from 8-20 carbon atoms and y is a positive number in the range 2-20 inclusive. 
     A process for making the above dyestuffs and their use as dispersing agents in the stabilization of dispersions of finely divided solids.

This application is a continuation-in-part of our application Ser. No.432,989 which was filed in the U.S. Patent Office 14th Jan., 1974, nowabandoned which was a continuation-in-part of our application Ser. No.219,843 which was filed in the U.S. Patent Office on 21st Jan., 1972,and was subsequently abandoned.

This invention relates to dyestuffs containing the residue of apolyester which are valuable as dispersing agents in the production ofdispersions of pigments in organic solvents.

According to the invention there are provided the dyestuffs of theformula:

    D--(Z-- O.OCR).sub. n

wherein D is the radical of a dyestuff which is attached to Z through acarbon atom of an aromatic ring present in D; Z is a divalent bridginggroup; n is a positive integer having a value of from 1 to 8; and R isthe radical of a carboxy ended polyester RCOOH derived from ahydroxycarboxylic acid of the formula:

    HO -- X -- COOH

wherein X is a divalent saturated or unsaturated aliphatic radicalcontaining at least 8 carbon atoms and in which there are at least 4carbon atoms between the hydroxy and carboxylic acid groups, or from amixture of such a hydroxycarboxylic acid and a carboxylic acid which isfree from hydroxy groups.

The dyestuff radical represented by D can be a radical of any of theknown dyestuff series, such as an azo or phthalocyanine radical but moreparticularly D is an anthraquinone radical. Anthraquinone compoundswhich are water soluble are not particularly suitable for thepreparation of the dispersing agents of the invention and it istherefore preferred that the anthraquinone compound used to prepare thedispersing agents is free from water solubilizing groups such as forexample sulphonic acid or carboxylic acid groups.

Where D is an azo or anthraquinone radical, n is preferably in the range1 to 4 and where D is a phthalocyanine radical n is preferably between 1and 5 inclusive. When n is 4 or less there may be only one side chain oneach of the benzene rings of the phthalocyanine radical but when n = 5or more, one or more of the benzene rings must contain at least 2 sidechains.

The bridging group Z can be more specifically represented by theformula:

    -- B --.sub.m A --

wherein B can be --NH--, --SO₂ NH-- or --CONH--, m can be 0 or 1 and Acan be alkylene, or β-hydroxy-alkylene, the alkylene group preferablycontaining less than 21 carbon atoms or monocyclicarylene-lower-alkylene, the term lower alkylene referring to alkylenegroups containing up to 4 carbon atoms. As examples of the alkyleneradicals represented by A there may be mentioned --CH₂ --, --CH₂ CH₂ --and --C₁₇ H₃₄ -- and as examples of the β-hydroxyalkylene radicals theremay be mentioned --CH₂ CHOH CH₂ --. As examples of thearylene-lower-alkylene radicals represented by A there may be mentionedtolylene, xylylene and p-dimethylene-phenylene.

The dyestuffs of this invention can be more specifically represented bythe formula:

    D -- Z -- O--OC--X--O).sub.y H].sub.n

or

    D -- Z -- O(OC--X--O).sub.(y-1) COT].sub.n

wherein D, Z, X and n have the above defined meanings, T is a saturatedor unsaturated aliphatic radical of from 8 to 20 carbon atoms, any y isa positive integer between 2 and 20.

According to a further feature of the invention there is provided aprocess for the manufacture of the dyestuffs of the invention ashereinbefore defined which comprises reacting a dyestuff compound of theformula:

    D -- z -- Y).sub.n

wherein D, Z and n have the meanings stated and Y is a chlorine or abromine atom, with one or more polyesters of the formula:

    HO(OC -- X -- O).sub.y H

or

    HO(OC -- X -- O).sub.(y-1) COT

where the former polyester is produced by the polymerisation of thehydroxy carboxylic acid HO--X--COOH and the latter polyester is producedby polymerisation of the hydroxy carboxylic acid HO--X--COOH in thepresence of the carboxylic acid T.COOH wherein, D, y, X and T have theabove defined meanings. Alternatively the free carboxylic acid group ofthe polyester (RCOOH) can be converted to an acid chloride (RCOCl) byreaction with for example thionyl chloride (SOCl₂) and the acid chloride(RCOCl) reacted with a dyestuff containing a free amino group DNH₂ toproduce a dispersant having the formula DNHCOR wherein D and R have themeanings defined hereinbefore.

The reaction between the dyestuff D(Z -- Y)_(n) or DNH₂ and thepolyester or polyester chloride (RCOCl) is carried out in the presenceof a quaternary ammonium compound and an acid binding agent.

The process of the invention can be conveniently carried out by stirringthe reactants together in an organic liquid, the reaction being carriedout at a temperature up to the boiling point of the reaction medium. Thereaction is preferably carried out under anhydrous conditions, and, inthe event that water is formed in the reaction or any of the reactantscontain water or are used in the form of aqueous solutions, it isadvisable to carry out the reaction at such a temperature that the waterpresent distils off from the reaction medium. At the conclusion of thereaction the organic liquid can be removed, for example by distillation;or the mixture may be filtered, the filtrate extracted with water toremove the quaternary ammonium or phosphonium compound and any inorganicsalts present, and then with a solvent such as isobutanol to remove anyunreacted polyester, and the organic liquid then removed, for example bydistillation or evaporation.

When the quaternary ammonium or phosphonium compound is a quaternaryammonium hydroxide then, provided that sufficient is present, this alsoacts as the acid-binding agent. However, the quaternary ammonium orphosphonium compound is normally used as a catalyst for the reaction, sothat whilst stoichiometric amounts can be added if desired, the use ofsuch large amounts is in fact unnecessary, and amounts in the region of1 to 30% based on the weight of dyestuff compound are adequate.

The polyesters used in the process of the invention can for example beobtained by heating the hydroxycarboxylic acid or a mixture of suchacids or a mixture of the hydroxycarboxylic acid and a carboxylic acid,optionally in the presence of an esterification catalyst, preferably ata temperature in the region of 160° to 200° C, until the requiredmolecular weight has been obtained. The course of the esterification canbe followed by measuring the acid value of the product, the preferredpolyesters having acid values in the range of 10 to 100 mgms KOH/gm andespecially in the range 20 to 50 mgms KOH/gm. The conditions ofpolymerisation are such that the acid value is a measure of the chainlength (y in the above formula) of the polyester. In the case of thepreferred polyesters an acid value of 10 mgms KOH/gm corresponds to apolyester containing 20 molecules of hydroxy carboxylic acid (i.e. y =20) whereas an acid value of 100 corresponds to a polyester containing 2molecules of hydroxy carboxylic acid (i.e. y = 2). The water formed inthe esterification reaction is removed from the reaction medium, andthis can be conveniently done by passing a stream of nitrogen over thereaction mixture or, preferably, by carrying out the reaction in thepresence of a solvent, such as toluene or xylene, and distilling off thewater as it is formed. The resulting polyesters can be isolated in theconventional manner.

In the said hydroxycarboxylic acids the radical represented by Xpreferably contains from 12 to 20 carbon atoms, and it is furtherpreferred that there are between 8 and 14 carbon atoms between thecarboxylic acid and hydroxy groups. It is also preferred that thehydroxy group is a secondary hydroxy group.

As specific examples of such hydroxycarboxylic acids there may bementioned ricinoleic acid, a mixture of 9- and 10-hydroxystearic acids(obtained by sulphation of oleic acid followed by hydrolysis), and12-hydroxystearic acid, and especially the commercially availablehydrogenated caster oil fatty acid which contains in addition to12-hydroxystearic acid minor amounts of stearic acid and palmitic acid.

The carboxylic acids which can be used in conjunction with thehydroxycarboxylic acids to obtain the polyesters are preferablysaturated or unsaturated aliphatic carboxylic acids, particularly alkyland alkenyl carboxylic acids containing a chain of from 8 to 20 carbonatoms. As examples of such acids there may be mentioned lauric acid,palmitic acid, stearic acid and oleic acid.

The dyestuff compounds which can be used in the process of the inventioncan themselves be prepared by standard known methods for theintroduction of groups of the formula: --Z--Y into dyestuff compounds.Thus, for example, chloromethyl or bromomethyl groups can be introducedby treating the appropriate dyestuff compound with formaldehyde orparaformaldehyde in the presence of hydrogen chloride, chlorosulphonicacid or hydrogen bromide. γ-chloro-β-hydroxypropylamino orγ-bromo-β-hydroxypropylamino groups can be introduced by reacting thecorresponding dyestuff containing an amino group with epichlorohydrin orwith epibromohydrin, and N-(chloro- or bromoalkyl)sulphoamido groups canbe introduced by treating the appropriate dyestuff compound withchlorosulphonic acid and reacting the resulting sulphonchloride with achloro- or bromo- alkylamine.

As specific examples of the said dyestuff compounds containing at leastone reactive chlorine or bromine atom there may be mentioned coppertris(chloromethyl)phthalocyanine,1:4-bis(γ-chloro-β-hydroxypropylamino)anthraquinone,2-methyl-4-N:N-di(β-hydroxyethyl)amino-4'-(N-β-chloroethylsulphonamido)-azobenzene,1-(γ-chloro-β-hydroxypropylamino)-4-[4'-β-hydroxyethoxy)phenylamino]-anthraquinone,copper mono(chloromethyl)phthalocyanine and copperpentakis-(chloromethyl)phthalocyanine.

As examples of acid-binding agents which can be used in the process ofthe invention there may be mentioned sodium carbonate and sodium orpotassium hydroxide.

As examples of organic liquids which can be used in the process theremay be mentioned ketones such as methyl isobutyl ketone, hydrocarbonliquids such as petroleum fractions, toluene and xylene, and halogenatedhydrocarbons with an unreactive halogen atom such as chlorobenzene.

As examples of quaternary ammonium or phosphonium compounds there may bementioned cetyl trimethylammonium bromide, tetraethyl ammoniumhydroxide,dodecyltrimethylammonium bromide and n-hexadecyl tri-n-propylphosphoniumbromide.

The dyestuffs of the invention are of value as dispersing agents inpreparing dispersions of pigments in organic liquids, and suchdispersions form a further feature of the invention. In preparing thedispersions it has been found that it is not essential to use puredyestuffs, since dyestuffs obtained by the process of the invention,which initially contain inorganic salts, quaternary ammonium orphosphonium compound and any unreacted polyester are equally suitable asit has been found that the presence of such compounds does not adverselyaffect the formation of the dispersions. Accordingly this reduces thecost of the dispersing agents by removing the necessity of purifyingthem. In fact when the dyestuff has been prepared in a suitable organicliquid medium the resulting solution of the dyestuff can be useddirectly for the preparation of the dispersion without even thenecessity to remove the organic liquid.

According to a further feature of the invention there are providedfinely divided dispersions of pigments in organic liquids which containdissolved therein a dyestuff containing at least one residue of apolyester as hereinbefore defined.

The said dispersions can be obtained by any of the conventional and wellknown methods of preparing dispersions. Thus the pigment, the organicliquid and the dyestuff may be mixed in any order and the mixture thensubjected to a mechanical treatment to reduce the particle size of thepigment, for example by ball milling, bead milling or gravel millinguntil the dispersion is formed. Preferably the mechanical treatment iscarried out until the particle size of the pigment is less than 20microns and preferably less than 10 microns.

If desired the dispersion can contain other substances, such as zincrosinate, which are conventionally present in dispersions of pigments inorganic liquids.

Alternatively, the pigment can be treated to reduce its particle sizeindependently or in admixture with either the organic liquid or thedyestuff, and the other ingredient or ingredients then added followingwhich dispersion can be obtained by stirring the mixture. As a furtheralternative an organic liquid solution of the dyestuff can be emulsifiedinto an aqueous phase by known means, such as high speed stirring, inthe presence of one or more surface active agents, and the resultingemulsion added to an aqueous slurry of the pigment, after which theorganic liquid and the water are removed by filtration and drying of theresidue of pigment and dyestuff. This residue can be subsequentlydispersed in an organic medium. Compositions obtained in this way andcomprising the pigment in finely divided form and the dyestuff are afurther feature of the invention.

It is preferred that the amount of dyestuff present in the dispersionsis such as corresponds to between 5 and 50% by weight, and preferablybetween 10 and 30%, based on the weight of the pigment, and thedispersions preferably contain from 5 to 70% by weight of the pigmentbased on the total weight of the dispersion.

The organic liquids used to prepare the said dispersions can be anyinert organic liquids in which the said dyestuffs are at least partlysoluble at ambient temperatures and which are stable under thesubsequent conditions of usage of the dispersion. If desired mixtures oforganic liquids can be used. Preferred organic liquids are hydrocarbonsand halogenated hydrocarbons such as benzene, toluene, xylene, whitespirit, n-hexane, cyclohexane, chlorobenzene, carbon tetrachloride, andperchloroethylene. Other organic liquids can however be used, forexample esters such as alkyd resins and heat bodied linseed oils used aslithographic varnish media. Above all it is preferred that the organicliquid is a predominantly aliphatic petroleum fraction. In general, theorganic liquids or mixtures thereof used to prepare the dispersions willdepend on the subsequent uses to which the dispersions are to be put.

The pigments can be either inorganic or organic pigments, and can be ofany of the recognised classes of pigments. As examples of inorganicpigments there may be mentioned titanium dioxide, carbon black, zincoxide, Prussian Blue, cadmium sulphide, iron oxides, vermillion,ultramarine and chrome pigments including chromates of lead, zinc,barium and calcium and the various mixtures and modifications thereofsuch as are commercially available as greenish-yellow to red pigmentsunder the name primrose, lemon, middle, orange, scarlet and red chromes.

As examples of organic pigments there may be mentioned pigments of theazo, thioindigo, anthraquinone, anthranthrone, isodibenzanthrone ortriphendioxazine series, vat dye pigments, phthalocyanine pigments suchas copper phthalocyanine and its nuclear halogenated derivatives andcopper tetraphenyl and octaphenyl phthalocyanines, quinacridone pigmentsand lakes of acid, basic and mordant dyestuffs. Such pigments aredescribed in, for example, volume 2 of the 2nd Edition of the ColourIndex which was published in 1956 under the heading "Pigments" and insubsequent authorised amendments thereto. Preferred pigments are carbonblack and especially copper phthalocyanine and its nuclear halogenatedderivatives. When the pigment is β-form copper phthalocyanine it may bethe normal pigmentary form of the copper phthalocyanine or it may becrude copper phthalocyanine.

The dyestuffs of the invention are particularly valuable for thepreparation of pigmentary dispersions of copper phthalocyanine directlyfrom crude copper phthalocyanine. A preferred class of the dyestuffs foruse in the pigment dispersions are those obtained by reactingchloromethylated copper phthalocyanine with the polyester, andparticularly with a polyester derived from 12-hydroxystearic acidoptionally containing minor amounts of stearic and/or palmitic acid.

The dispersions of the invention are fluid or semi-fluid compositionscontaining the pigment in finely divided and deflocculated form, and canbe used for any purpose for which dispersions of these particular solidsare conventionally used. Thus the dispersions are of particular value inthe manufacture of printing inks, by incorporating the dispersions withthe other components conventionally used in the manufacture of suchinks. The dispersions are also of value in the manufacture of paints,for which purpose the dispersions are incorporated into conventionalalkyd or other resins. Alternatively, the dyestuffs of the invention canbe used as dispersing agents in the production of dispersions of otherdyestuffs, such as Acid Dyestuffs, Disperse Dyestuffs and BasicDyestuffs, in organic liquids, such dispersions being used for thesolvent dyeing of textiles.

The invention is illustrated but not limited by the following Examplesin which the parts and percentages are by weight.

Polyesters were prepared as follows:

Polyester A

A mixture of 348 parts of xylene and 3350 parts of a commercial grade of12-hydroxystearic acid (having acid and hydroxyl values of 182mg.KOH/gm. and 160 mg.KOH/gm. respectively) is stirred for 22 hours at190° to 200° C, the water formed in the reaction being separated fromthe xylene in the distillate which is then returned to the reactionmedium. After 152 parts of water have been collected, the xylene isremoved by heating at 200° C in a stream of nitrogen. The resulting paleamber coloured liquid has an acid value of 33.0 mgms KOH/gm. Since thecommercial starting material is a mixture of the 12-hydroxy and thehydroxy-free stearic acid Polyester A consists of a mixture ofpolyesters of the general formulae ##STR1## where, from the acid value,it can be calculated that the average value of y = 6.2.

Polyester B

A mixture of 130 parts of xylene, 126 parts of stearic acid and 716parts of 12-hydroxystearic acid is heated for 22 hours at 190° C to 200°C, the water formed in the reaction being separated from the xylene inthe distillate which is then returned to the reaction mixture. Thexylene is then removed by heating at 180° C at a pressure less thanatmospheric. The residual liquid is cooled to 50° C, and equal volume ofa petroleum fraction boiling in the range of 100° to 120° C is added,the mixture cooled to 10° C and the mixture filtered to remove stearicacid. The solvent is then removed by distillation at 100° C underreduced pressure, leaving the polyester in the form of a pale ambercoloured viscous liquid having an acid value of 58.6 mgms KOH/gm.Polyester B is a mixture of polyesters of the same general formulae asPolyester A except that from the acid value it is calculated that theaverage value of y = 3.3.

Polyester C

A mixture of 65 parts of xylene and 500 parts of a commerciallyavailable grade of ricinoleic acid is heated for 22 hours at 190° C to200° C, the water being distilled off as it is formed. The xylene isthen removed by distillation at 150° C at reduced pressure. Theresulting polyester has an acid value of 13.7 mgms KOH/gm.

Since the commercial starting material is a mixture of ricinoleic acidand oleic acid Polyester C consists of a mixture of polyesters of thegeneral formulae ##STR2## where, from the acid value, it can becalculated that the average value of y = 14.6.

Polyester D

A mixture of 96 parts of xylene, 150 parts of oleic acid and 850 partsof ricinoleic acid is heated for 22 hours at 190° to 200° C, the waterbeing distilled off as it is formed. The xylene is then removed bydistillation at 150° C under reduced pressure. The resulting polyesterhas an acid value of 36.6 mgms. KOH/gm.

Polyester D is a mixture of polyester of the same general formulae asPolyester C except that from the acid value it is calculated that theaverage value of y = 5.4.

Polyester E

A mixture of 706 parts of 12-hydroxystearic acid, 489 parts of stearicacid and 2.5 parts of tetrabutyl titanate is stirred at 190° to 200° Cfor 5 hours in a current of nitrogen. 100 Parts of the product aredissolved while still hot in 147 parts of a petroleum fraction boilingat 100° to 120° C. After cooling in ice and filtering, the solution isevaporated at 100° , finally under reduced pressure (water pump),leaving 79.7 parts of an oil of acid value 83.3 mg KOH/g. Polyester E isa mixture of polyesters of the same general formulae as Polyester Aexcept that from the acid value it is calculated that the average valueof y = 2.4.

EXAMPLE 1

A mixture of 44.3 parts of Polyester A, 15.3 parts of a 25% aqueoussolution of tetraethylammonium hydroxide, 6 parts of coppertris(chloromethyl) phthalocyanine and 72 parts of methyl isobutylketoneis stirred for 16 hours at the boil under a reflux condenser fitted witha trap to remove the water. The methyl isobutylketone is then distilledoff under reduced pressure leaving the crude dyestuff as a deep blueviscous liquid.

EXAMPLE 2

A mixture of 44.3 parts of Polyester A, 9.5 parts of a commerciallyavailable grade of cetyl trimethylammonium bromide, 72 parts of methylisobutyl ketone, 3.4 parts of a 32% aqueous solution of sodium hydroxideand 6 parts of copper tris(chloromethyl) phthalocyanine is stirred for16 hours under reflux condenser fitted with a trap to remove the water.The solvent is then removed in a current of nitrogen leaving the crudeproduct as a deep blue viscous liquid.

EXAMPLE 3

The procedure of Example 2 is repeated except that only 1 part of thecetyl trimethylammonium bromide is used. A similar product is obtained.

EXAMPLE 4

A mixture of 44.3 parts of Polyester A, 1 part of the cetyltrimethylammonium bromide, 1.4 parts of sodium carbonate, 6 parts ofcopper tris(chloromethyl)phthalocyanine and 64 parts of a petroleumfraction boiling at 100° to 120° C is stirred for 16 hours at the boilunder a reflux condenser fitted with a trap to remove the water. Thesolution is cooled and is decanted from a little solid matter. Thesolution contains 47.9% of crude dyestuff.

EXAMPLE 5

A mixture of 54 parts of Polyester B, 2 parts of thecetyltrimethylammonium bromide, 2.8 parts of sodium carbonate, 12 partsof copper tris(chloromethyl)phthalocyanine and 64 parts of a petroleumfraction boiling at 100° to 120° C is stirred for 16 hours under areflux condenser at 111° C, the water present being separated using atrap. The resulting solution containing 54.0% of crude dyestuff is thendecanted from a trace of solid matter.

EXAMPLE 6

A mixture of 53.5 Polyester C, 0.5 part of the cetyl trimethylammoniumbromide, 0.7 part of sodium carbonate, 3 parts of coppertris(chloromethyl)phthalocyanine and 64 parts of a petroleum fractionboiling at 100° to 120° C is stirred for 16 hours at the boil under areflux condenser fitted with a trap to remove water. The resultingsolution containing 53.9% of crude dyestuff is then decanted from atrace of solid matter.

EXAMPLE 7

A mixture of 40 parts of Polyester D, 1 part of the cetyltrimethylammonium bromide, 1.4 parts of sodium carbonate, 6 parts ofcopper tris(chloromethyl)phthalocyanine and 64 parts of a petroleumfraction boiling at 100° to 120° C. is stirred for 16 hours at the boilunder a reflux condenser fitted with a trap to remove water. Theresulting solution containing 47.7% of crude dyestuff is then decantedfrom a trace of solid matter.

EXAMPLE 8

A mixture of 36.2 parts of a polyester having an acid value of 35.5 mgmsKOH/gm. prepared from a commercial grade of 12-hydroxystearic acid, 0.76part of the cetyl trimethylammonium bromide, 1.06 parts of sodiumcarbonate, 4.55 parts of copper tris(chloromethyl) phthalocyanine and 18parts of a petroleum fraction boiling at 100° to 120° C. is stirred for16 hours at the boil under a reflux condenser fitted with a trap toremove water. The solution is then filtered to remove a trace of solidmaterial. The solution contains 69.6% of crude dyestuff.

EXAMPLE 9

The procedure of Example 8 is repeated but after filtering to remove thetrace of solid material, the filtrate is successively extracted with (a)water, (b) acetone, (c) isobutanol (several times) and (d) acetone, andis then dried. The resulting product is in the form of a dark blue tar.

The infra red absorption spectrum of the dyestuff shows no bands at2500-3500 cm⁻ ¹ and 1712 cm⁻ ¹ (due to --COOH groups and which wereclearly visible in the I.R. absorption spectrum of the polyester used asstarting material), nor at 1600 cm⁻ ¹ due to --COO⁻ groups; but bands at1730 cm⁻ ¹ and 1180 cm⁻ ¹ indicate the presence of ester groups.

EXAMPLE 10

A mixture of 40 parts of the polyester used in Example 8, 0.8 part ofthe cetyl trimethylammonium bromide, 1.2 parts of sodium carbonate, 10parts of1-(γ-chloro-β-hydroxypropylamino)-4-[4'-(β-hydroxyethoxy)anilino]anthraquinoneand 71 parts of a petroleum fraction boiling at 100° to 120° C. isstirred for 16 hours at the boil under a reflux condenser fitted with atrap to remove water. The solvent is then removed by heating at 140° C.in a current of nitrogen, leaving the crude product in the form of adark blue viscous liquid.

EXAMPLE 11

In place of the anthraquinone compound used in Example 10 there is used10 parts of2-methyl-4-N:N-di(β-hydroxyethyl)amino-4'-(N-β-chloroethylsulphonamido)-azobenzene.The resulting product is a deep brown viscous liquid.

EXAMPLE 12

In place of the anthraquinone compound used in Example 10 there is used10.7 parts of1-(β-hydroxyethylamino)-4-[2'-bromo-4'-(N-β-chloroethylsulphonamido)phenylazo]-naphthalene.The product is a deep red viscous liquid.

EXAMPLE 13

A mixture of 18.2 parts of the polyester used in Example 8, 0.4 part ofthe cetyltrimethylammonium bromide, 0.55 part of sodium carbonate, 6parts of copper mono(chloromethyl)phthalocyanine and 35.5 parts of apetroleum fraction boiling at 100° to 120° C. is stirred for 16 hours atthe boil under a reflux condenser fitted with a trap to remove water.The solvent is then removed in a current of nitrogen leaving a deep bluetar.

EXAMPLE 14

A mixture of 36.3 parts of the polyester used in Example 8, 0.76 part ofthe cetyl trimethylammonium bromide, 1.06 parts of sodium carbonate,3.04 parts of copper pentakis(chloromethyl)-phthalocyanine and 35.5parts of a petroleum fraction boiling at 100° to 120° C. is stirred for16 hours at the boil under a reflux condenser fitted with a trap toremove water. The solvent is then removed in a stream of nitrogenleaving a deep blue viscous liquid.

EXAMPLE 15

A mixture of 3 parts of β-form copper phthalocyanine, 0.6 part of thedyestuff of Example 9 and 6.4 parts of a petroleum fraction boiling at100° to 120° C. is ball milled for 16 hours to give a finely dividedwell deflocculated dispersion of the pigment which is suitable for usein a gravure printing ink.

Similar finely divided well deflocculated dispersions are obtained whenthe 0.6 part of the dyestuff of Example 9 is replaced by 0.6 part ofeach of the dyestuffs of Examples 1, 2, 3 and 14 or by using suchquantities of the dyestuff solutions of Examples 4, 5 and 8 as contain0.6 part of crude dyestuff.

EXAMPLE 16

A mixture of 3 parts of β-form copper phthalocyanine, 1.5 parts of thedyestuff of Example 10 and 5.5 parts of a petroleum fraction boiling at100° to 120° C. is milled for 16 hours to to give a finely divided welldeflocculated dispersion of the pigment suitable for use in a gravureprinting ink.

The following Table gives further Examples of dispersions which areobtained by milling together, in the quantities stated, the pigmentslisted in the second column of the Table, the dyestuffs or dyestuffsolutions listed in the third column of the Table and the organicliquids listed in the fourth column of the Table. In each case finelydivided well deflocculated dispersions of the pigments were obtained.

    __________________________________________________________________________    Example                                                                            Pigment             Dyestuff or Dyestuff Solution                                                                    Organic Liquid                    __________________________________________________________________________    17   3 parts of the pigment obtained by                                                                1.5 parts of the dyestuff of                                                                     5.5 parts of a petroleum               coupling tetrazotised 3:3'-dichloro-                                                              Example 11         fraction boiling at                                                           100°                            benzidine with acetoacetanilide        to 120° C.                 18   3 parts of 1-(2'-nitro-4'-methyl-                                                                 1.5 parts of the dyestuff of                                                                     "                                      phenylazo)-2-naphthol                                                                             Example 12                                           19   3 parts of β-form copper                                                                     1.5 parts of the dyestuff of                                                                     "                                      phthalocyanine      Example 13                                           20   "                   2.8 parts of the dyestuff                                                                        4.2 parts of a petroleum                                   solution of Example 6                                                                            fraction boiling at                                                           100°                                                                   to 120° C                  21   "                   3.1 parts of the dyestuff                                                                        3.9 parts of a petroleum                                   solution of Example 7                                                                            fraction boiling at                                                           100°                                                                   to 120° C.                 22   3 parts of indanthrone                                                                            0.9 part of the dyestuff                                                                         6.1 parts of a petroleum                                   solution of Example 8                                                                            fraction boiling at                                                           100°                                                                   to 120° C.                 23   3 parts of a rosinated calcium                                                                    "                  "                                      toner of 1-(2'-sulpho-4'-methyl-                                              phenylazo)-2-naphthol-3-carboxylic                                            acid                                                                     24   3 parts of lead sulphochromate                                                                    "                  "                                 25   3 parts of a nickel toner of 3-                                               (4'-chlorophenylazo)quinoline                                                                     "                  "                                      2:4-diol                                                                 26   3 parts of Prussian Blue                                                                          "                  "                                 27   3 parts of an aluminium lake of                                                                   0.9 part of the dyestuff solution                                                                6.1 parts of a petroleum               1:4-dihydroxyanthraquinone-2-                                                                     of Example 8       fraction boiling at                                                           100°                            sulphonic acid                         to 120° C.                 28   3 parts of Tioxide RCR which is a                                                                 "                  "                                      coated form of rutile titanium                                                dioxide                                                                  29   Iron oxide          "                  "                                 30   3 parts of carbon black                                                                           "                  "                                 31   3 parts of copper polychloro-                                                                     "                  "                                      phthalocyanine                                                           32   3 parts of 4:10-dibromoanthan-                                                                    "                  "                                      throne                                                                   33   3 parts of the phosphomolybdo-                                                                    "                  "                                      tungstate of C.I. Basic Blue 7                                                (42595)                                                                  34   3 parts of β-form copper                                                                     1.5 parts of the dyestuff of                                                                     5.5 parts of n-hexane                  phthalocyanine      Example 1                                            35   "                   "                  5.5 parts of cyclohexane          36   "                   "                  5.5 parts of                      __________________________________________________________________________                                                xylene                        

EXAMPLE 37

A mixture of 60 parts of crude copper phthalocyanine. 15 parts of thedyestuff of Example 3 and 125 parts of a petroleum fraction boiling at100° to 120° C. is ball milled to give a fluid deflocculated dispersionof the copper phthalocyanine containing no particles greater than 3 μand the majority of the particles being less than 1 μ.

The dispersion is suitable for use in gravure printing inks and showsincreased strength, enhanced finish and greenness compared withconventional dispersions of β-form copper phthalocyanine.

EXAMPLE 38

25 Parts of β-form copper phthalocyanine, 5 parts of the dyestuff ofExample 3 and 10 parts of a petroleum fraction boiling at 260° to 290°C. are charged to a mixer of the Baker-Perkins type and plastic milledfor 60 minutes. A further 3.6 parts of the same petroleum fraction areadded and mixing continued for a further 15 minutes to give ahomogeneous viscous paste. The paste, which contains 57.5% of pigment,is suitable for use in letterpress printing inks.

EXAMPLE 39

60 Parts of a furnance grade carbon black having a surface area of 80sq. meters/gm., 15.7 parts of the dyestuff solution of Example 4, 74.3parts of a petroleum fraction boiling at 100° C to 120° C. and 500 partsof 6 mm diameter steatite balls are charged to a container which issealed and then placed on a roller mill which is operated for 24 hoursat 100 r.p.m. The contents of the container are then passed through asieve to remove the balls. The product is a free flowing paste of finelydispersed carbon black.

When this paste is mixed with a gravure ink varnish such as a solutionof zinc/calcium rosinate in a hydrocarbon solvent, a black gravure inkis obtained which has good gloss and tinctorial properties and in whichthe carbon black is finely dispersed.

EXAMPLE 40

A mixture of 10 parts of1:5-dihydroxy-4:8-diamino-2-(p-hydroxyphenyl)-6-hydroxymethylanthraquinone4.2 parts of the dyestuff solution of Example 4 and 160 parts ofperchloroethylene is ball milled for 16 hours to give a welldeflocculated dispersion of the anthraquinone dyestuff which can be usedfor the solvent dyeing of aromatic polyester textile materials.

EXAMPLE 41

A mixture of 7.2 parts of the dyestuff solution of Example 8, 2.8 partsof perchloroethylene and 0.5 part of an adduct of a mixture of oleyl andcetyl alcohols with 2.5 mols of ethylene oxide is added to a solution of2 parts of an adduct of cetyl alcohol with 17 mols of ethylene oxide in194 parts of water containing 6 parts of sulphuric acid, and the wholeis emulsified by high speed agitation.

5 Parts of crude copper phthalocyanine is milled in the presence of awater-soluble inorganic salt, the salt is removed by washing and theresulting α-form copper phthalocyanine is heated in 100 parts of dilutesulphuric acid to dissolve metallic impurities. 42 Parts of the aboveemulsion are added at 60° C., the mixture stirred for 15 minutes, theslurry filtered and the pigment washed with water and dried.

An ink is prepared by grinding 1.08 parts of the dried pigment with 0.92part of a synthetic letterpress litho printing ink varnish (viscousalkyd medium). The ink is much less viscous than a control ink which wassimilarly prepared from the crude copper phthalocyanine except that noemulsion was added to the pigment slurry, and prints made from this inkhave equal strength, but greater brightness, compared with prints madefrom the control ink.

EXAMPLE 42

A mixture of 36.3 parts of the polyester used in Example 8, 0.76 part ofthe cetyl trimethylammonium bromide, 1.06 parts of sodium carbonate,5.15 parts of a chloromethylatedp:p'-di(6-methylbenzthiazol-2-yl)azobenzene containing 13.1 % ofchlorine and 36 parts of a petroleum fraction boiling at 100° to 120° Cis stirred for 16 hours at the boil under a reflux condenser fitted witha trap to remove water. The solvent is then removed at 110° C in acurrent of nitrogen leaving the crude dye stuff in the form of a browngum.

EXAMPLE 43

A mixture of 3 parts of the pigment obtained by coupling tetrazotised3:3'-dichloro-4:4'-diaminodiphenyl with acetoacetanilide, 0.6 part ofthe dyestuff of Example 42 and 6.4 parts of a petroleum fraction boilingat 100° to 120° C is ball milled for 16 hours to give a finely divided,well deflocculated dispersion of the pigment.

EXAMPLE 44

A mixture of 36.3 parts of the polyester used in Example 8, 0.76 part ofn-hexadecyl tri-n-propylphosphonium bromide, 1.06 parts of sodiumcarbonate, 4.55 parts of copper tris(chloromethyl)-phthalocyanine and 36parts of a petroleum fraction boiling at 100° to 120° C is stirred for16 hours at the boil under a reflux condenser fitted with a trap toremove water. The solvent is then removed at 110° C in a stream ofnitrogen leaving the crude dyestuff as a deep blue viscous liquid.

EXAMPLE 45

A mixture of 3 parts of β-form copper phthalocyanine, 0.6 part of thedyestuff of Example 44 and 6.4 parts of a petroleum fraction boiling at100° to 120° C is ball milled for 16 hours to give a finely divided,well deflocculated dispersion of the pigment.

EXAMPLE 46

96 Parts of crude copper phthalocyanine, 24 parts of the dyestuff ofExample 3, 12.8 parts of zinc rosinate and 167.2 parts of a petroleumfraction boiling at 100° to 120° C are stirred together in a stainlesssteel vessel equipped with a stirrer having 3 discs each 10 cms. indiameter and 8 mms. in thickness. 1000 Parts of glass beads having adiameter of 0.6 to 0.7 mm. are added and the mixture stirred for 60minutes at 1880 r.p.m. After this time the dispersion contains nosignificant number of pigment particles having a size above 3 microns,and the majority of the pigment particles are less than 1 micron. Thepigment dispersion is then separated from the glass beads.

The resulting dispersion consists essentially of a β-form copperphthalocyanine pigment dispersion of high tinctorial strength and whichpossesses greenness and brightness of shade when used in a gravureprinting ink.

EXAMPLE 47

A mixture of 64 parts of crude copper phthalocyanine, 16 parts of thedyestuff of Example 3, 12.8 parts of zinc rosinate and 107.2 parts of apetroleum fraction boiling at 100° to 120° C is ball milled to give afluid, deflocculated dispersion of the copper phthalocyanine having noparticles greater than 3 microns and the majority of the particles beingless than 1 micron.

This dispersion is suitable for use in gravure printing inks and givesinks of increased strength, enhanced finish and greenness compared withinks prepared from conventional dispersions of β-form copperphthalocyanine.

EXAMPLE 48

A mixture of 31.6 parts of Polyester A, 37 parts of a petroleum fractionboiling at 100° to 120° C, 0.75 part of cetyl trimethylammonium bromide,1.05 parts of sodium carbonate and 4 parts of1,4-bis(γ-chloro-β-hydroxypropylamino)-anthraquinone is stirred whilst 7parts of the petroleum fraction are distilled out. The mixture is thenboiled under reflux for 16 hours. The petroleum fraction is finallydistilled out at 120° C in a current of nitrogen, leaving the crudedyestuff as a viscous blue tar.

EXAMPLE 49

A mixture of 3 parts of β-form copper phthalocyanine, 1.5 parts of thedyestuff of Example 48 and 5.5 parts of a petroleum fraction boiling at100° to 120° C is ball milled for 16 hours to give a finely divideddeflocculated dispersion of the pigment.

EXAMPLE 50

A mixture of 30.2 parts of Polyester A, 0.72 part of a commerciallyavailable grade of cetyl trimethylammonium bromide, 1.2 parts of sodiumcarbonate, 6.7 parts of a sulphonamide prepared as described below and39 parts of toluene is stirred for 16 hours at the boil under a refluxcondenser fitted with a trap to remove the water. The resulting solutioncontains 58.3% of crude dyestuff.

The sulphonamide used above is prepared as follows. 357 Parts ofchlorosulphonic acid are stirred whilst 65 parts of copperphthalocyanine are added below 50° C. After stirring for 16 hours at138°-140° C it is cooled to 90° C and 94.5 parts of phosphorustrichloride are added during 1 hour. It is then stirred for 2 hours at90°-93° C and cooled. 92 Parts of this solution are added to excess ice,the precipitated sulphonyl chloride is filtered off and washed with icecold water. 28 parts of N-(3-chloro-2-hydroxypropyl)-p-toluidine aredissolved in 158 parts of isopropanol at 30°-35° C. 12 parts of sodiumbicarbonate are added, followed by the sulphonyl chloride filter cake.After stirring at 20° C for 16 hours, 600 parts of water are added andthe sulphonamide is filtered off and washed with water. It is thenstirred with a mixture of 29 parts of hydrochloric acid and 250 parts ofwater for 10 minutes to dissolve unreacted amine, after which thesulphonamide is filtered off, washed acid-free and dried at 20° C. Itcontains 10% of chlorine. The infra red spectrum shows bands at 1350 and1162 cm⁻ ¹ due to sulphonamide groups.

EXAMPLE 51

A mixture of 3 parts of β-form copper phthalocyanine, 1.28 parts of the58.3% dyestuff solution of Example 50 and 5.72 parts of a petroleumfraction boiling at 100° to 120° C is ball milled for 16 hours to give afinely divided well deflocculated dispersion of the pigment.

EXAMPLE 52

A mixture of 23 parts of Polyester A, 28.2 parts of a petroleum fractionboiling at 100° to 120° C, 0.5 part of cetyl trimethylammonium bromide,0.76 part of sodium carbonate and 3.9 parts of1,4-bis-(m-chloromethylbenzoylamino)-anthraquinone is stirred for 16hours at the boil under a reflux condenser fitted with a trap to removewater. The resulting solution contains 50% of crude dyestuff.

EXAMPLE 53

A mixture of 23 parts of Polyester A, 28.5 parts of a petroleum fractionboiling at 100° to 120° C, 0.5 part of cetyl trimethylammonium bromide,0.76 part of sodium carbonate and 4.25 parts of 1-(α-chloroacetylamino)-anthraquinone is stirred for 16 hours at the boil under a refluxcondenser fitted with a trap to remove water. The resulting solutioncontains 50% of crude dyestuff.

EXAMPLE 54

A mixture of 23 parts of Polyester A, 30.4 parts of a petroleum fractionboiling at 100° to 120° C, 0.54 part of cetyl trimethylammonium bromide,0.76 part of sodium carbonate and 6.08 parts of1-(α-chloroacetylamino)-4-benzoylamino-anthraquinone is stirred for 16hours at the boil under a reflux condenser fitted with a trap to removewater. The petroleum fraction is distilled off as xylene is graduallyadded. After boiling under reflux for a further 2 hours, 67 parts of a45.4% solution of crude dyestuff is obtained.

EXAMPLE 55

A mixture of 31.7 parts of xylene, 23 parts of Polyester A, 0.76 part ofsodium carbonate, 0.54 part of cetyl trimethylammonium bromide and 7.8parts of 1-chloroacetylamino-5,8-bis(benzoylamino)-anthraquinone isstirred for 16 hours at the boil under a reflux condenser fitted with atrap to remove water. The xylene is then removed by evaporation leavingthe crude dyestuff as a viscous liquid.

EXAMPLE 56

A mixture of 25.9 parts of xylene, 23 parts of Polyester A, 0.76 part ofsodium carbonate, 0.54 part of cetyl trimethylammonium bromide and 1.99parts of 1,4,5,8-tetrakis-(chloroacetylamino)-anthraquinone is convertedto the dyestuff as described in Example 55.

EXAMPLE 57

A mixture of 28.6 parts of xylene, 23 parts of Polyester A, 0.76 part ofsodium carbonate, 0.54 part of cetyl trimethylammonium bromide and 4.77parts of 4,4'-bis-(chloroacetylamino)-1,1'-dianthraquinonylamine isconverted to the dyestuff as described in Example 55.

EXAMPLE 58

A mixture of 81.6 parts of Polyester C, 5.27 parts of1,4-bis-(m-chloromethylbenzoylamino)-anthraquinone, 1.06 parts of sodiumcarbonate, 0.76 part of cetyl trimethylammonium bromide and 88 parts ofa petroleum fraction boiling at 100° to 120° C is stirred for 16 hoursat the boil under a reflux condenser fitted with a trap to remove water.The resulting solution contains 50% of crude dyestuff.

EXAMPLE 59

A mixture of 26.4 parts of xylene, 23 parts of Polyester A, 0.76 part ofsodium carbonate, 0.54 part of cetyl trimethylammonium bromide and 2.51parts of 1,4-bis-(2'-chloroethylamino)-anthraquinone is converted to thedyestuff as described in Example 55.

EXAMPLE 60

A mixture of 14.8 parts of a petroleum fraction boiling at 100° to 120°C, 9.7 parts of Polyester E, 0.76 part of sodium carbonate, 0.5 part ofcetyl trimethylammonium bromide and 4.25 parts of1-(α-chloroacetylamino)-anthraquinone is stirred for 16 hours at theboil under a reflux condenser fitted with a trap to remove water. Afurther 22 parts of the petroleum fraction is added and the 35.5%solution of the crude dyestuff decanted from a small quantity ofundissolved solid.

EXAMPLE 61

A mixture of 108 parts of Polyester A, 15 parts of 2-aminoanthraquinoneand 16.4 parts of thionyl chloride is stirred at 100° to 105° C for 5hours then toluene is gradually added and simultaneously distilled offto remove unchanged thionyl chloride. The residual toluene is evaporatedoff leaving the crude dyestuff as a gum.

EXAMPLE 62

A mixture of 35 parts of Polyester A, 5 parts of4,4'-diamino-1,1'-dianthraquinonylamine and 6.6 parts of thionylchloride is stirred at 100°-110° C for 16 hours then toluene isgradually added and simultaneously distilled off to remove unchangedthionyl chloride. The residual toluene is evaporated off leaving thecrude dyestuff as a gum.

EXAMPLE 63

A mixture of 28.5 parts of toluene, 23 parts of Polyester A, 0.76 partof sodium carbonate, 0.55 part of cetyl trimethylammonium bromide and4.66 parts of 1,4-dianilinoanthraquinonebis-(sulphon-β-chloroethylamide) is stirred for 16 hours at the boilunder a reflux condenser fitted with a trap to remove water. The tolueneis then evaporated, leaving the crude dyestuff as a blue gum.

EXAMPLE 64

A mixture of 3 parts of β-form copper phthalocyanine, 6 parts of thedyestuff solution of Example 52 and 1 part of a petroleum fractionboiling at 100° to 120° C is ball milled for 16 hours to give a finelydivided well deflocculated dispersion of the pigment.

The following Table gives further examples of finely divided welldeflocculated dispersions which are obtained by milling together, in thequantities stated, the pigments listed in the second column of theTable, the dyestuffs or dyestuff solutions listed in the third column ofthe Table and the organic liquids listed in the fourth column of theTable.

    __________________________________________________________________________                                Dyestuff or    Organic                            Example                                                                             Pigment               Dyestuff solution                                                                            Liquid                             __________________________________________________________________________    65    3 parts of β-form copper phthalocyanine                                                        3 parts of the Dyestuff                                                                      4 parts of a petroleum                                         Solution of Example 52                                                                       fraction boiling at                                                           100° to 120° C.      66    "                     3 parts of the Dyestuff                                                                      1 part of a petroleum                                          Solution of Example 53                                                                       fraction boiling at                                                           100° to 120 C.              67    3 parts of a rosinated calcium toner                                                                3 parts of the Dyestuff                                                                      4 parts of a petroleum                   of 1-(2'-sulpho-4'-methylphenylazo)-                                                                Solution of Example 52                                                                       fraction boiling at                      2-naphthol-3-carboxylic acid         100° to 120° C.      68    3 parts of lead sulphochromate                                                                      3 parts of the Dyestuff                                                                      "                                                              Solution of Example 53                            69    3 parts of a nickel toner of                                                                        "              "                                        3-(4'-chlorophenylazo)-quinoline-                                             2,4-diol                                                                70    3 parts of Tioxide RCR which is a                                                                   "              "                                        coated form of rutile titanium dioxide                                  71    3 parts of flavanthrone                                                                             "              "                                  72    3 parts of an aluminium lake of                                                                     1.5 parts of the dyestuff                                                                    5.5 parts of a petroleum                 1,4-dihydroxy-anthraquinone-2-                                                                      of Example 48  fraction boiling at                                                           100°                              sulphonic acid                       to 120° C.                  73    3 parts of copper polychloro-                                                                       "              "                                        phthalocyanine                                                          74    3 parts of indanthrone                                                                              1.5 parts of the dyestuff                                                                    5.5 parts of a                                                 of Example 48  petroleum fraction                                                            boiling at 100° to                                                     120° C.                     75    3 parts of 8, 18-dichloro-5,15-                                                                     "              "                                        diethyldi-indolo(3,2-b,3',2'-m)-5,15                                          dehydrotriphendioxazine                                                 76    3 parts of carbon black                                                                             "              "                                  77    3 parts of the phospho-molybdotungstate                                                             "              "                                        of C.I. Basic Blue 7 (42595)                                            78    3 parts of the pigment obtained by                                                                  3 parts of the dyestuff                                                                      4 parts of a                             coupling tetrazotised 3,3'-dichloro-                                                                of Example 53  petroleum fraction                       benzidine with acetoacetanilide      boiling at 100° to                                                     120° C.                     79    3 parts of β-form copper phthalocyanine                                                        3.3 parts of the dyestuff                                                                    3.7 parts of a                                                 solution of Example 54                                                                       petroleum fraction                                                            boiling at 100° to                                                     120° C.                     80    3 parts of β-form copper phthalocyanine                                                        1.5 parts of the dyestuff                                                                    5.5 parts of a                                                 of Example 55  petroleum fraction                                                            boiling at 100° to                                                     120° C.                     81    "                     1.5 parts of the dyestuff                                                                    "                                                              solution of Example 56                            82    3 parts of β-form copper                                                                       1.5 parts of the dyestuff                                                                    5.5 parts of a                           phthalocyanine        of Example 57  petroleum fraction                                                            boiling at 100° to                                                     120° C.                     83    "                     3 parts of the dyestuff                                                                      4 parts of a                                                   solution of Example 58                                                                       petroleum fraction                                                            boiling at 100° to                                                     120° C.                     84    3 parts of copper polychloro-                                                                       1.5 parts of the dyestuff                                                                    5.5 parts of a                           phthalocyanine        of Example 59  petroleum fraction                                                            boiling at 100° to                                                     120° C.                     85    "                     4.2 parts of the dyestuff                                                                    2.8 parts of a                                                 solution of Example 60                                                                       petroleum fraction                                                            boiling at 100° to                                                     120° C.                     86    3 parts of β-form copper phthalocyanine                                                        1.5 parts of the dyestuff                                                                    5.5 parts of a                                                 of Example 61  petroleum fraction                                                            boiling at 100° to                                                     120° C.                     87    "                     1.5 parts of the dyestuff                                                                    "                                                              of Example 62                                     88    "                     1.5 parts of the dyestuff                                                                    "                                                              of Example 63                                     __________________________________________________________________________

What we claim is:
 1. A dyestuff selected from the classes of dyestuffrepresented by the formulae

    D -- Z -- O -- OC -- X -- O).sub.y H].sub.n

    D -- Z -- O -- OC -- X -- O).sub.(y.sub.-1) COT].sub.n

or mixtures thereof wherein D is an anthraquinone radical which is freefrom water solubilising groups and which is attached to Z through acarbon atom on one of the benzene rings present in D; n is 1 to 4; Z isa linking group of the formula -- B)_(m) A -- wherein B is --NH--, --SO₂NH-- or --CO--NH--, m is 0 or 1 and A is alkylene or β-hydroxy-alkylenecontaining up to 20 carbon atoms or monocyclic arylene-lower-alkylene, Xis alkylene or alkenylene containing from 8 to 20 carbon atoms with atleast 4 carbon atoms between the --CO-- and --O-- groups, T is alkyl oralkenyl containing from 8 to 20 carbon atoms and y is a positive integerbetween 2 and
 20. 2. A dyestuff according to claim 1 represented by theformulae

    D -- Z -- O--OC -- X -- O).sub.(y.sub.-1) COT].sub.n

wherein B is --NH--.
 3. A dyestuff according to claim 2 having theformula ##STR3##
 4. A dyestuff according to claim 1 comprising a mixtureof ##STR4## and ##STR5##